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WO2012020743A1 - Procédé pour la fabrication d'hydrocarbure insaturé, et catalyseur de déshydrogénation utilisé dans ledit procédé - Google Patents

Procédé pour la fabrication d'hydrocarbure insaturé, et catalyseur de déshydrogénation utilisé dans ledit procédé Download PDF

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WO2012020743A1
WO2012020743A1 PCT/JP2011/068098 JP2011068098W WO2012020743A1 WO 2012020743 A1 WO2012020743 A1 WO 2012020743A1 JP 2011068098 W JP2011068098 W JP 2011068098W WO 2012020743 A1 WO2012020743 A1 WO 2012020743A1
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Prior art keywords
catalyst
hydrocarbon
zinc
unsaturated hydrocarbon
producing
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English (en)
Japanese (ja)
Inventor
パラー ヘン
真一郎 市川
石川　淳一
裕一 池永
川原　潤
康秀 後安
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Priority to SG2013009980A priority Critical patent/SG187797A1/en
Priority to US13/816,343 priority patent/US20130158328A1/en
Priority to KR1020137003096A priority patent/KR101514580B1/ko
Priority to CN201180039002.6A priority patent/CN103068774B/zh
Priority to JP2012528676A priority patent/JP5564115B2/ja
Priority to EP11816407.8A priority patent/EP2604590A4/fr
Publication of WO2012020743A1 publication Critical patent/WO2012020743A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/86—Borosilicates; Aluminoborosilicates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/08—Alkenes with four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/12—Alkadienes
    • C07C11/16—Alkadienes with four carbon atoms
    • C07C11/167—1, 3-Butadiene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/324—Catalytic processes with metals
    • C07C5/325—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/22—After treatment, characterised by the effect to be obtained to destroy the molecular sieve structure or part thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/44—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/86—Borosilicates; Aluminoborosilicates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1081—Alkanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/22—Higher olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method for producing an unsaturated hydrocarbon corresponding to the hydrocarbon by contacting the hydrocarbon with a specific dehydrogenation catalyst, and a dehydrogenation catalyst used in the production method.
  • Unsaturated hydrocarbons obtained by hydrocarbon dehydrogenation are useful as basic raw materials in the petrochemical industry.
  • propylene, 1-butene, 2-butene, isobutene, styrene, butadiene and the like can be given as examples.
  • the propylene is an important industrial raw material used as a synthetic raw material for acrylonitrile, polypropylene, ethylene propylene rubber, propylene oxide, acetone, isopropyl alcohol and octanol.
  • the aforementioned 1-butene and 2-butene are raw materials for producing propylene by a metathesis reaction with ethylene, and in the middle of butadiene (which is useful as a raw material for synthetic rubber for automobile tires), which has been in great demand in recent years. It is also extremely useful as a body.
  • butadiene is a typical diene compound, and is used as a raw material for synthetic rubber such as SBR (styrene butadiene rubber) or NBR (acrylonitrile butadiene rubber), a raw material for ABS (acrylonitrile butadiene styrene) resin and nylon 66, and the like. ing.
  • isobutene which is a kind of unsaturated hydrocarbon, is useful as a raw material for polyisobutylene, methacrolein, methyl methacrylate, methyl-tert-butyl ether, ethyl-tert-butyl ether, dibutylhydroxytoluene, dibutylhydroxyanisole and the like.
  • styrene produced by dehydrogenation of ethylbenzene is useful as a raw material for polystyrene, which is a general-purpose resin.
  • the hydrogen obtained by the hydrocarbon dehydrogenation reaction of the present invention can be used as an energy source as it is, or is an extremely useful product as an intermediate for producing petrochemical products.
  • hydrocarbons are dehydrogenated in the presence of a specific catalyst to produce unsaturated hydrocarbons (especially olefins and / or dienes) corresponding to the hydrocarbons.
  • a specific catalyst to produce unsaturated hydrocarbons (especially olefins and / or dienes) corresponding to the hydrocarbons.
  • the technology is known.
  • Examples of the catalyst for performing dehydrogenation include a catalyst containing chromium oxide, a catalyst containing platinum-tin, a catalyst containing platinum-zinc, and a catalyst containing iron.
  • a catalyst containing chromium oxide has a very short catalyst life, and chromium is highly toxic (see, for example, Non-Patent Documents 1 to 3).
  • platinum-zinc catalyst As the platinum-zinc catalyst, a technique using silicalite substantially free of alkali as a support (for example, see Patent Document 1) or a technique using borosilicate (for example, see Patent Documents 2 to 6) as a support. It has been reported that these platinum-zinc catalysts have a relatively long catalyst life compared to a catalyst containing chromium oxide and a catalyst containing platinum-tin.
  • Patent Document 7 As the iron-containing catalyst, a technique using an iron oxide catalyst containing an alkali metal has been reported (for example, see Non-Patent Document 5). However, these catalyst systems have low activity and particularly low reactivity. When applied to hydrocarbons, there was a problem that reaction conditions had to be severe. Also disclosed is an example in which deboronated borosilicate is used as a support for oxidative dehydrogenation or oxidation reaction catalyst. (For example, Patent Document 7)
  • the present invention is a method for producing an unsaturated hydrocarbon corresponding to a hydrocarbon by dehydrogenating a hydrocarbon using a safe catalyst having a long catalyst life, and is suitably used for such a production method. It is an object to provide a catalyst that can be used.
  • the present inventors have used a silicate obtained by removing at least a part of boron atoms from a borosilicate as a support, and the support supports zinc and a Group VIIIA metal. It was found that the catalyst thus produced has a significantly longer catalyst life than the conventional dehydrogenation catalyst, and can produce unsaturated hydrocarbons with a conversion rate and selectivity equivalent to those of the conventional catalyst. It came to be completed.
  • the present invention provides a catalyst obtained by supporting zinc and a Group VIIIA metal on a silicate obtained by removing at least a part of boron atoms from a borosilicate, and a hydrocarbon to contact the hydrocarbon.
  • the residual amount of boron atoms in the silicate is preferably 80% or less of the total amount of boron atoms in the borosilicate, and the amount of zinc in the catalyst A is 0.01 to 15 masses.
  • the amount of the Group VIIIA metal in the catalyst A is preferably 0.01 to 5% by mass, and the borosilicate is preferably an MFI-type zeolite.
  • Group VIIIA metal examples include palladium, nickel, platinum, rhodium, ruthenium, iridium, etc. Among these, platinum is preferably used.
  • hydrocarbons as a production raw material in the production method of the present invention include hydrocarbons having 2 to 20 carbon atoms, particularly preferably propane, n-butane, isobutane, n-butene, isopentane and ethylbenzene. It is.
  • the unsaturated hydrocarbon produced by the production method of the present invention is preferably an olefin and / or diene useful as an industrial raw material.
  • the catalyst A and the hydrocarbon are preferably contacted at a reaction temperature of 300 to 800 ° C., and the reaction pressure is preferably 0.01 to 1 MPa.
  • the contact between the catalyst A and the hydrocarbon is preferably carried out in the presence of water, and the amount of water used at this time is 0.05 to 20 mole times the hydrocarbon. Is preferred.
  • Catalyst A for dehydrogenating hydrogen to produce an unsaturated hydrocarbon corresponding to the hydrocarbon is also included in the scope of the present invention.
  • a method for producing a corresponding unsaturated hydrocarbon by dehydrogenating a hydrocarbon using a catalyst having a long catalyst life, that is, having a low frequency of catalyst regeneration and excellent in operability is provided.
  • FIG. 1 is a visual representation of the difference in catalyst life (effect of deboronation atoms) of the catalysts used in Example 1, Example 6, Comparative Example 1 and Comparative Example 2.
  • FIG. 2 shows the catalyst used in Example 2 (without water coexisting in the reaction system), Example 3 (water coexisting in the reaction system) and Comparative Example 3 (water coexisting in the reaction system). This is a visual representation of the difference in catalyst life (effect of water addition to the reaction system).
  • the catalyst A used in the method for producing unsaturated hydrocarbons of the present invention (hereinafter also simply referred to as “the production method of the present invention”) is a silicate obtained by removing at least a part of boron atoms from a borosilicate. And a catalyst obtained by supporting zinc and a Group VIIIA metal.
  • the borosilicate used for obtaining the catalyst A is not particularly limited as long as it is a silicate containing a boron atom. Some of such borosilicates have a crystalline type and an amorphous type structure. From the viewpoint of catalytic reaction efficiency and catalyst life, crystalline borosilicate is preferable.
  • Crystalline borosilicate has a zeolite structure, and examples of the structure of zeolite include MFI type, BEA type, MWW type, CON type and FAU type. Among these, MFI-type zeolite (borosilicate) is preferable because it is easily available.
  • the aluminum content in the crystalline borosilicate (zeolite) used in the present invention is not particularly limited, but the silica / alumina ratio in the borosilicate is preferably 100 or more, more preferably 500 or more. , 1000 or more, particularly preferably 2000 or more, and usually 400000 or less, which is the limit of substantial analysis accuracy.
  • the oligomerization reaction of the unsaturated hydrocarbon that is a product in the production method of the present invention proceeds, and the oligomer becomes coke. Accumulation on the catalyst A may shorten the catalyst life. Moreover, if the silica / alumina ratio is 400,000 or less, the object of the present invention can be sufficiently achieved.
  • the content of alkali metal and alkaline earth metal in the crystalline borosilicate (zeolite) used in the present invention is not particularly limited. However, if a large amount of alkali such as potassium is contained in the catalyst A, the dehydrogenation reaction may be adversely affected. For this reason, it is desirable that alkali metal and alkaline earth metal are not substantially present in the borosilicate. “Substantially absent” means that the concentration of alkali metal and alkaline earth metal in the borosilicate is 300 ppm or less, respectively.
  • the content of boron atoms contained in the borosilicate before removing at least part of the boron atoms is not particularly limited, but is preferably 100 to 30000 ppm, more preferably 500 to 10000 ppm, and particularly preferably 1000 to 8000 ppm. .
  • borosilicate before removing boron atoms It must contain a certain amount of boron atoms.
  • the boron atom content can be measured by, for example, an analysis method using ICP (inductively coupled plasma) (ICP-AES).
  • ICP-AES inductively coupled plasma
  • the borosilicate described above can be easily produced by a known method, and can also be obtained from a catalyst manufacturer.
  • the borosilicate described above may be used alone or in combination of two or more.
  • ⁇ Removal of boron atom from borosilicate> at least a part of boron atoms is removed from the borosilicate to obtain a silicate having a reduced boron atom content, and this is used as a carrier for supporting zinc and a Group VIIIA metal described later. To do.
  • lattice defects such as atomic vacancies are generated in the resulting silicate (which usually contains a certain amount of boron atoms).
  • This lattice defect is considered to greatly contribute to the improvement of the dispersibility of zinc and the Group VIIIA metal in the catalyst A, which will be described later, and to improve the catalyst life.
  • the lattice defects and zinc and the Group VIIIA metal have some interaction, for example, the lattice defects, zinc and the Group VIIIA metal are fixed on the silicate carrier as hetero atoms, By stabilizing, it is considered that aggregation of metal, which is one of the causes of catalyst deactivation, hardly occurs.
  • the boron atom remaining rate in the silicate after removing at least part of the boron atoms from the borosilicate is the entire boron atoms contained in the borosilicate before removing the boron atoms from the viewpoint of improving the catalyst life.
  • the amount (100% by weight) is preferably 80% or less, more preferably 50% or less, particularly preferably 30% or less, and most preferably 20% or less.
  • the boron atom residual ratio can be calculated by comparing the boron atom content in the borosilicate before removing the boron atom and the boron atom content in the silicate after removing the boron atom.
  • the boron atom content can be measured by an analysis method using ICP as described above.
  • a method for removing at least a part of boron atoms from the borosilicate As a method for removing at least a part of boron atoms from the borosilicate, a method of treating with an aqueous solution of an inorganic acid or an organic acid, a method of treating with an inorganic acid or an organic acid solution dissolved in an organic solvent (the solvent is other than water) Is mentioned. Among these, from the viewpoint of safety and production cost, a method of treating with an aqueous solution of an inorganic acid or an organic acid is desirable.
  • Examples of the inorganic acid include nitric acid, sulfuric acid, and hydrochloric acid, and examples of the organic acid include acetic acid and oxalic acid.
  • Examples of the organic solvent include methanol and ethanol.
  • the treatment of borosilicate with these acidic aqueous solutions and the like is usually performed at room temperature of 25 ° C to 200 ° C.
  • treatment at a high temperature is preferable.
  • treatment at a high temperature is effective for improving the removal efficiency of boron atoms, but in order to perform the treatment at a temperature of 100 ° C. or higher, it is necessary to use an autoclave, and the operation becomes complicated. It is preferable to carry out at less than 100 ° C.
  • the treatment is immersing borosilicate in an acidic aqueous solution or the like.
  • concentration of the acid aqueous solution or the like is preferably 0.01 to 15 N (equivalent / L) from the viewpoint of boron atom removal efficiency.
  • the acidic aqueous solution may be a single acid solution or a mixture of two or more acid solutions.
  • the treatment time depends on the treatment temperature, the amount of boron atoms in the borosilicate, the removal ratio, and the like, and cannot be generally stated, but is usually 1 to 24 hours. In some cases, treatment with an acidic aqueous solution or the like is repeated.
  • filtration and filtration may be performed and the filter cake obtained may be fired. Firing may be performed in one stage or in multiple stages including two or more stages.
  • heating is usually performed at 400 to 600 ° C. for 1 to 10 hours.
  • the first stage is heated at 80 to 150 ° C. for 0.5 to 5 hours, and the second stage is heated at 400 to 600 ° C. for 1 to 10 hours.
  • the "Group VIIIA metal” is a notation of the old IUPAC method, and in terms of the IUPAC method, it is a metal of Group 8 to 10.
  • Examples of the Group VIIIA metal include platinum, palladium, ruthenium, iridium, rhodium and nickel. Among these, platinum is preferable as the metal supported on the silicate from the viewpoint of catalytic activity.
  • the zinc and Group VIIIA metal can be supported on the silicate using a metal compound such as a corresponding metal nitrate, metal chloride or metal complex.
  • the silicate can be supported by a known method such as an ion exchange method or an impregnation method.
  • Examples of the zinc compound include zinc nitrate, zinc chloride, and zinc acetate.
  • Examples of the Group VIIIA metal compound include chloroplatinic acid, tetraammineplatinum chloride, tetraammineplatinum hydroxide, tetraammineplatinum nitrate, and tetraammineplatinum. Examples include tetrachloroplatinic acid.
  • Firing may be performed in one stage, or may be performed in multiple stages including two or more stages.
  • a silicate carrying zinc or the like is heated at 400 to 600 ° C. for 1 to 10 hours.
  • the silicate when firing in two stages, is usually heated at 80 to 150 ° C. for 0.5 to 5 hours in the first stage and heated at 400 to 600 ° C. for 1 to 10 hours in the second stage.
  • the atmosphere at the time of firing is not particularly limited as long as it is a gas not containing a reducing gas, but the firing is usually carried out under the circulation of air.
  • the order of supporting the metal on the silicate is not particularly limited. It is possible to support zinc on a silicate using a zinc compound and then support the silicate using a Group VIIIA metal compound, and conversely, after supporting using a Group VIIIA metal compound, It is also possible to support using a zinc compound. Further, the zinc compound and the Group VIIIA metal compound may be used simultaneously, and the zinc and the Group VIIIA metal compound may be simultaneously supported on the silicate.
  • the amount of zinc supported in the catalyst A used in the production method of the present invention obtained by carrying out such loading is 0. 0% relative to the entire catalyst A (100% by mass) from the viewpoint of catalyst life and catalyst efficiency.
  • the content is preferably 01 to 15% by mass, more preferably 0.05 to 5% by mass, and particularly preferably 0.1 to 3% by mass.
  • the amount of the Group VIIIA metal supported on the catalyst A is preferably 0.01 to 5% by mass with respect to the entire catalyst A (100% by mass) from the viewpoint of catalyst life and catalyst efficiency. It is more preferably from 3 to 3% by mass, particularly preferably from 0.1 to 1.5% by mass.
  • the zinc and the Group VIIIA metal preferably have a metal molar ratio (Zn / VIIIA) of 0.5 or more. If it is less than 0.5, the catalyst life is short, and if it is too high, the activity becomes low and the by-products increase. Usually, it is 0.5 to 50, preferably 1 to 30, and more preferably 1 to 20.
  • the loading amount in the catalyst A is the ratio of the weight of the metal compound used for loading in terms of metal atoms to the total weight of the catalyst A, and the metal (zinc and The amount of (Group VIIIA metal) supported can be directly measured by, for example, an analysis method using ICP.
  • zinc and a Group VIIIA metal are supported on the silicate obtained by removing at least a part of boron atoms from the borosilicate.
  • a plurality of types of metals may be used (supported) as the Group VIIIA metal.
  • the aforementioned catalyst A is charged into the reactor in the following form. That is, the catalyst obtained by the above method is essentially in a fine powder state.
  • the obtained fine powder catalyst may be charged into the reactor as it is, but in order to prevent an increase in pressure loss, the above decomposition may be molded by the following method and then charged.
  • the powdery catalyst may be filled with an inert filler such as silica balls or alumina balls.
  • the obtained fine powder catalyst may be molded and filled after kneading with a sintering agent binder (binder) which does not change the catalyst performance.
  • the sintering agent is typically a silica type, but can be selected from any one of an alumina type, a titania type, a zirconia type, and a diatom degree type.
  • the soot sintering is preferably performed in the range of 500 to 800 ° C.
  • the shapes to be molded are Tablets, Extrusions, Pellets, Spheres, Microspheres, CDS Extrusions, Trilobes, and Quadrobes. Examples include (Quardlobes), ring (Ring), 2 spoke ring (2 Sporkes rings), special spoke rings such as HGS, EW, LDP, rib ring (Rib rings), and crushed fold (Granules).
  • the molding process considering that the physical properties and catalyst performance of the molded catalyst A are not impaired, the molding process is possible, the binder content is adjusted, and as a molding aid, a thickener, Many substances such as surfactants, water retention agents, plasticizers, and binder materials are used. In consideration of the reactivity of these substances, it is preferable to perform the molding process at an appropriate stage of the above-described catalyst manufacturing process. For example, after forming the borosilicate powder, the boron atoms are removed and the metal is loaded, the boron boron is removed from the boron, the formation is carried out, the metal is loaded, the boron is removed from the boron, and the metal is loaded. , Removal of boron atoms from borosilicate, loading of zinc, forming, and loading of VIIIA.
  • hydrocarbon In the method for producing an unsaturated hydrocarbon of the present invention, a hydrocarbon corresponding to the unsaturated hydrocarbon, that is, a hydrocarbon obtained by hydrogenating a double bond existing in the unsaturated hydrocarbon is used as a raw material. .
  • the hydrocarbon usually a hydrocarbon having 2 to 20 carbon atoms is used.
  • the skeleton structure of the hydrocarbon is not particularly limited, and may be either linear or branched.
  • straight chain hydrocarbons include ethane, propane, n-butane, n-butene, n-pentane, n-pentene, n-hexane, n-hexene, n-heptane, n-heptene, ethylbenzene and cumene.
  • Examples of the branched hydrocarbon include isobutane, isobutene, isopentane, isopentene, 2-methylpentane, 2-methylpentene, 3-methylpentane, and 2,2-dimethylbutane.
  • propane, n-butane, n-butene, isobutane, isopentane and ethylbenzene are particularly preferred from the viewpoint of obtaining industrially useful unsaturated hydrocarbons by the formation of double bonds by dehydrogenation reaction.
  • Propane is mainly produced from propane, 1-butene, 2-butene and isobutene are produced from n-butane, butadiene is produced from n-butene, isobutene is produced from isobutane, isoprene is produced from isopentane, and styrene is produced from ethylbenzene. .
  • Examples include fractions containing butane and butene obtained, fractions containing pentane obtained after separating isoprene and pentene from C5 fraction, and fractions containing pentane and pentene obtained after separating isoprene from C5 fraction. be able to.
  • the fraction used again as a raw material in the naphther cracking furnace or the fraction used as a fuel can be used as a raw material. Further, LPG gas that can be easily obtained as a fuel can be used as a raw material.
  • raw materials may be used alone, or may be used by mixing them in an arbitrary amount.
  • the raw material is not limited to the above, and may contain other components (impurities) as long as they contain a hydrocarbon having 2 to 20 carbon atoms as long as the effects of the present invention are not impaired.
  • the other components include hydrogen, carbon monoxide, carbon dioxide gas, methane, and dienes.
  • a raw material containing a plurality of hydrocarbons having 2 to 20 carbon atoms when used, it can be used after separating a part of the raw material by a known separation method, or it can be used as it is without separation.
  • olefin and diene products can be separated and purified.
  • LPG gas is a mixture of propane, n-butane and isobutane.
  • propane, n-butane or isobutane can be distilled and purified and used as a raw material.
  • propane, n-butane or isobutane can be distilled and purified and used as a raw material.
  • it can be used as a raw material as it is, and olefins and dienes can be separated after dehydrogenation.
  • the hydrocarbon is a reducing substance
  • the metal zinc and the Group VIIIA metal
  • An alloy is formed from zinc and a Group VIIIA metal. This alloy is considered to have high catalytic performance for the dehydrogenation reaction.
  • the catalyst A can be used in a reduced state by pretreatment with a reducing gas such as hydrogen or carbon monoxide before being used for hydrocarbon dehydrogenation.
  • a reducing gas such as hydrogen or carbon monoxide
  • the reducing gas may be used without being diluted, or may be appropriately diluted with water or nitrogen.
  • the catalyst A can be used for hydrocarbon dehydrogenation, but the initial stage of the reaction (the state in which the activity of the catalyst A is low because very little metal is reduced and activated) ) Is shortened by pretreatment with a reducing gas such as hydrogen or carbon monoxide.
  • a reducing gas such as hydrogen or carbon monoxide.
  • the contact temperature between the catalyst A and the hydrocarbon that is, the reaction temperature of the dehydrogenation reaction is preferably 300 to 800 ° C., more preferably 400 to 700 ° C., more preferably 450 to 650 ° C. from the viewpoint of reaction efficiency. Particularly preferred is 480 to 620 ° C.
  • the reaction temperature of the dehydrogenation reaction occurs in the gas phase.
  • reaction temperature If the reaction temperature is low, the equilibrium conversion rate of hydrocarbons is low, and the yield of unsaturated hydrocarbons in one pass tends to be small. Moreover, when reaction temperature is too high, there exists a tendency for the coking speed
  • the reaction pressure of the dehydrogenation reaction is preferably 0.01 to 1 MPa, more preferably 0.05 to 0.8 MPa, and more preferably 0.1 to 0.5 MPa from the viewpoint of reaction efficiency. It is particularly preferred.
  • the amount of catalyst A used is simply and appropriately expressed by the weight space velocity WHSV.
  • the feed rate of hydrocarbons to catalyst A is not particularly limited, but the feed rate at which WHSV (the feed amount of hydrocarbons per unit amount of catalyst A and unit time) is in the range of 0.01 to 50 h ⁇ 1. More preferably, the speed is such that WHSV is in the range of 0.1 to 20 h ⁇ 1 .
  • the amount of the hydrocarbon and catalyst A used is appropriately selected in a more preferable range depending on the reaction temperature of the dehydrogenation reaction or the activity of the catalyst A, and the reaction can be carried out based on the range.
  • the reaction may be performed in the presence of other components other than the hydrocarbon and the catalyst A as long as the method does not contradict the purpose and does not impair the effects of the present invention.
  • components for example, water, oxides such as methane, hydrogen and carbon dioxide can be cited as preferred examples, and water is particularly preferred.
  • the present inventors have found that the presence of water during the dehydrogenation reaction dramatically improves the life of the catalyst. This is presumably because water has the effect of suppressing the coking rate on the catalyst A and suppressing the volatilization of zinc from the catalyst A.
  • the amount of water present in the dehydrogenation reaction is preferably 0.05 to 20 moles, and preferably 0.3 to 10 moles, relative to the hydrocarbon as the raw material (water / hydrocarbon). More preferred is 0.5 to 5 mole times. If the amount of water present is too small, the effect of suppressing the coking rate on the catalyst A and the like may not be exhibited, and the catalyst life may be shortened. Moreover, when there is too much addition amount of water, thermal efficiency may fall and reaction efficiency on an energy basis may fall.
  • the methane may be used as a reaction diluent to create the same state as when the reaction system is depressurized, thereby improving the equilibrium conversion rate.
  • the hydrogen and carbon dioxide may be able to extend the life of catalyst A.
  • reaction format used in the method for producing an unsaturated hydrocarbon of the present invention is not particularly limited, and a known format can be adopted.
  • reaction formats that can be employed include reaction formats such as fixed bed, moving bed, and fluidized bed. From the viewpoint of ease of process design, a fixed bed system is particularly preferable.
  • the unsaturated hydrocarbon produced by the production method of the present invention is preferably an olefin (unsaturated hydrocarbon having one double bond in one molecule) and a diene (double) from the viewpoint of industrial usefulness. Unsaturated hydrocarbon having two bonds in one molecule). That is, the production method of the present invention is preferably a production method of olefin and / or diene.
  • Particularly preferred compounds produced by the production method of the present invention are propylene, 1-butene, 2-butene, isobutene, butadiene, isoprene and styrene, which are produced from propane, n-butane, isobutane, n-butene, isopentane and ethylbenzene. It is. Also, butadiene and isoprene can be produced simultaneously from butane and isopentane. Such a method for producing a diene is also included in the present invention. As described above, these are industrially useful raw materials.
  • the catalyst A used in the production method of the present invention has a longer catalyst life than that of the conventional dehydrogenation catalyst, and the catalyst life is further dramatically improved by allowing water to coexist in the reaction system. become longer.
  • the method of the present invention provides a catalyst having excellent operability, which requires less frequent catalyst regeneration, and has improved the olefin and / or diene production method to an industrial level.
  • the amount of boron atoms in the obtained silicate powder was 260 ppm (boron atom residual ratio: about 8%) as determined by ICP-AES.
  • Synthesis Example 2 Preparation of Zinc-Supported Silicate (Zeolite) 0.33 g of an aqueous solution containing 0.0810 g (0.272 mmol) of zinc nitrate hexahydrate with respect to 1 g of the silicate obtained in Synthesis Example 1 was added and impregnated with zinc ions by the Incipient-Wetness method.
  • the powder After impregnating the solution, the powder was sufficiently mixed and further baked in air at 120 ° C. for 3 hours and at 500 ° C. for 4 hours to prepare a silicate on which zinc was supported.
  • the powder After impregnating the solution, the powder was sufficiently mixed and then calcined in air at 120 ° C. for 3 hours and further at 500 ° C. for 4 hours to prepare a silicate (catalyst 1) carrying platinum and zinc. .
  • Synthesis Example 4 Preparation of borosilicate (catalyst 2) on which platinum and zinc are supported
  • Synthesis Example 2 instead of using a silicate (zeolite) from which boron atoms have been removed, no boron atom removal treatment was performed.
  • a borosilicate carrying zinc was obtained in the same manner as in Synthesis Example 2 except that a borosilicate having an MFI structure containing 3200 ppm of boron atoms prepared by the method of Synthesis Example 11 described later was used.
  • the powder was sufficiently mixed and then calcined in air at 120 ° C. for 3 hours and further at 500 ° C. for 4 hours to prepare a zeolite carrying zinc.
  • Synthesis Example 6 Preparation of a silicate (catalyst 3) on which platinum and zinc are supported Instead of using the silicate on which zinc obtained in Synthesis Example 2 is supported, a zeolite on which zinc obtained in Synthesis Example 5 is supported A silicate (catalyst 3) on which platinum and zinc were supported was prepared in the same manner as in Synthesis Example 3 except that the above was used.
  • Synthesis Example 7 Preparation of MFI-type silicalite (catalyst 4) on which platinum and zinc are supported Instead of using a silicate (zeolite) from which a part of boron atoms has been removed in Synthesis Example 2, it has boron atoms from the beginning.
  • Synthesis Example 5 instead of using a silicate (zeolite) from which a part of boron atoms has been removed, boron atoms are not removed, that is, 3200 ppm of boron atoms prepared by the method of Synthesis Example 11 described later is contained.
  • a borosilicate carrying zinc was obtained in the same manner as in Synthesis Example 5 except that a borosilicate having an MFI type structure was used.
  • the amount of boron atoms in the obtained silicate powder was 170 ppm as determined by ICP-AES (the residual ratio of boron atoms was about 4%).
  • Synthesis Example 10 Preparation of silicate (catalyst 7) supporting platinum and zinc
  • 180 ml of 3N nitric acid aqueous solution was used instead of 900 ml, and the filter cake was washed with distilled water 300 ml. Was done only once.
  • the amount of boron atoms in the obtained silicate powder was 1300 ppm as determined by ICP-AES (boron atom residual ratio: about 40%).
  • the platinum content (supported amount) and zinc content (supported amount) in the catalyst 7 were analyzed by ICP-AES, and were found to be 0.32% by mass and 1.78% by mass, respectively.
  • the obtained powder was put into 3 L of 1 mol / L ammonium nitrate aqueous solution, stirred at 80 ° C. for 3 hours, filtered and washed.
  • the aqueous solution of ammonium nitrate was again treated, and the filtered and washed solid was dried at 120 ° C. for 4 hours and further baked at 540 ° C. for 6 hours to obtain a white powder.
  • This white powder was confirmed to have an MFI type crystal structure by X-ray powder diffraction measurement.
  • the composition of the borosilicate having the MFI type structure was quantified by ICP-AES and ICP-MS. As a result, the boron atom content was 3200 ppm and the silica / alumina ratio was 200000.
  • Table 1 summarizes the properties of Catalysts 1 to 7 prepared by the synthesis methods 1 to 11 described above.
  • the measurement procedure is shown below. After 0.1 g of each catalyst was put in a U-shaped glass sample tube and mounted on a carbon monoxide adsorption apparatus, the gas phase portion of the sample tube was purged with helium gas at room temperature, and then replaced with hydrogen gas. As a pretreatment, the temperature was raised to 600 ° C. in 30 minutes under a hydrogen flow, and further maintained at 600 ° C. for 2 hours to reduce the catalyst.
  • the mixture was cooled to 50 ° C. under the flow of helium gas, and a pulse of helium gas containing 10% by volume of carbon monoxide was introduced into the catalyst layer 5 times.
  • the amount of carbon monoxide in the gas after flowing through the catalyst layer was quantified with a thermal conductivity detector.
  • defects caused by the removal of boron atoms which is the method of the present invention, have the effect of improving the dispersibility of the supported metal.
  • defects other than the removal of boron atoms cause defects in zeolite crystals. If it is a thing, the same effect can be anticipated even if it does not use especially a borosilicate as a precursor.
  • Example 1 The catalyst 1 obtained in Synthesis Example 3 was charged into a tubular reactor (SUS tube) having a diameter of 1 ⁇ 2 inch and a total length of 300 mm equipped with an inner tube of alumina having an inner diameter of 6 mm, and the gap was quartz. Filled with sand.
  • SUS tube tubular reactor
  • the reactor was connected to a flow reactor, and after flowing nitrogen, hydrogen was circulated (20 ml / min), and the temperature was raised to 600 ° C. in an electric furnace. After the internal temperature of the reactor reached 600 ° C., the catalyst 1 was reduced with hydrogen for 2 hours.
  • the reaction was performed at 0.15 MPa.
  • the product after a predetermined time shown in Table 2 below was analyzed by an on-line gas chromatograph. The line from the reactor outlet to the gas chromatograph was kept at 220 ° C.
  • Quantification of the product was performed by an absolute calibration curve method using a gas chromatograph equipped with a flame ionization detector and a gas chromatograph equipped with a thermal conductivity detector. Table 2 below shows the results of analyzing the product.
  • butane conversion rate ((concentration of n-butane in raw material + concentration of isobutane in raw material) ⁇ (concentration of n-butane in product + concentration of isobutane in product)) / (concentration of n-butane in raw material + raw material) Isobutane concentration)
  • Butene selectivity (1-butene concentration in the product + 2-butene concentration in the product + isobutene concentration in the product) / ((n-butane concentration in the raw material + isobutane concentration in the raw material) ⁇ (production N-butane concentration in the product + isobutane concentration in the product-hydrogen concentration in the product))
  • Butadiene selectivity butadiene concentration in the product / ((n-butane concentration in the raw material + is
  • Example 2 A dehydrogenation reaction was performed in the same manner as in Example 1 except that the catalyst 3 obtained in Synthesis Example 6 was used instead of the catalyst 1 obtained in Synthesis Example 3.
  • Table 3 shows the results of analyzing the product.
  • Example 3 A dehydrogenation reaction was performed in the same manner as in Example 2 except that n-butane / water mixed gas was fed to the reactor instead of n-butane and the reaction pressure was 0.1 MPa.
  • Table 4 shows the results of analyzing the product.
  • Example 4 A dehydrogenation reaction was performed in the same manner as in Example 3 except that the catalyst 6 obtained in Synthesis Example 9 was used instead of the catalyst 3 obtained in Synthesis Example 6.
  • Table 5 shows the results of analyzing the product.
  • Example 5 A dehydrogenation reaction was performed in the same manner as in Example 3 except that an n-butene / water mixed gas was fed to the reactor instead of the n-butane / water mixed gas.
  • Table 6 shows the results of analyzing the product.
  • Example 5 as a result of analyzing carbon monoxide and carbon dioxide in the product at a reaction time of 25 hours, the selectivity based on weight was 1.7% carbon monoxide and 0.8% carbon dioxide. It is presumed that the catalyst life is prolonged by coke, which is a cause of a decrease in catalyst activity, being oxidized by water and converted into carbon monoxide and carbon dioxide.
  • Example 6 A dehydrogenation reaction was performed in the same manner as in Example 1 except that the catalyst 7 was used instead of the catalyst 1. Table 7 below shows the results of analyzing the product.
  • Example 7 A dehydrogenation reaction was carried out in the same manner as in Example 3 except that the reaction temperature was 450 ° C. As a result of analyzing the product, an n-butene yield of 26%, which is an equilibrium value, was obtained. When the reaction was carried out for 120 hours or more, there was no decrease in yield. The selectivity was 98%.
  • FIG. 1 shows a visual representation of the difference in catalyst life of the catalysts used in Example 1, Example 6, Comparative Example 1 and Comparative Example 2.
  • FIG. 2 shows a visual representation of the difference between the two.
  • a catalyst having a longer catalyst life than a conventionally used catalyst for dehydrogenation reaction is used, and it is useful as an unsaturated hydrocarbon, preferably an industrial raw material. Olefin and / or diene can be produced.
  • propylene that can be produced by the production method of the present invention is used as a synthetic raw material such as acrylonitrile, polypropylene, ethylene propylene rubber, propylene oxide, acetone, isopropyl alcohol, and octanol.
  • 1-butene and 2-butene are useful as raw materials for sec-butyl alcohol, butadiene and propylene
  • Isobutene is a very useful substance used as a raw material for polyisobutylene, methacrolein, methyl methacrylate, methyl-tert-butyl ether, ethyl-tert-butyl ether, dibutylhydroxytoluene and dibutylhydroxyanisole
  • Butadiene produced using 1-butene and 2-butene as an intermediate is used as a raw material for synthetic rubber such as SBR or NBR, ABS resin, and nylon 66.
  • styrene produced by dehydrogenation of ethylbenzene is useful as a raw material for polystyrene, which is a general-purpose resin.
  • the number of times of catalyst regeneration can be reduced, and the life of the catalyst can be greatly extended by allowing water to coexist in the reaction system. Therefore, according to the present invention, it is expected that the degree of freedom in the process design and equipment design of the dehydrogenation reaction is increased, and it is possible to produce unsaturated hydrocarbons more advantageously industrially.
  • the production method of the present invention is excellent from the viewpoint of safety.

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Abstract

[Problème] Décrire un procédé dans lequel un catalyseur sûr ayant une durée de vie catalytique plus longue qui est utilisé pour déshydrogéner un hydrocarbure et fabriquer un hydrocarbure insaturé correspondant à l'hydrocarbure. [Solution] La présente invention concerne un procédé pour fabriquer un hydrocarbure insaturé qui correspond à un hydrocarbure est caractérisé en ce qu'il comprend une étape pour déshydrogéner l'hydrocarbure en provoquant le contact entre l'hydrocarbure et un catalyseur (A) obtenu en fixant du zinc et un métal du groupe VIIIA sur un silicate, le silicate étant obtenu en éliminant au moins certains des atomes de bore d'un borosilicate.
PCT/JP2011/068098 2010-08-12 2011-08-09 Procédé pour la fabrication d'hydrocarbure insaturé, et catalyseur de déshydrogénation utilisé dans ledit procédé Ceased WO2012020743A1 (fr)

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SG2013009980A SG187797A1 (en) 2010-08-12 2011-08-09 Method for manufacturing unsaturated hydrocarbon, and dehydrogenation catalyst used in said method
US13/816,343 US20130158328A1 (en) 2010-08-12 2011-08-09 Process for producing unsaturated hydrocarbons and dehydrogenation catalyst used in the process
KR1020137003096A KR101514580B1 (ko) 2010-08-12 2011-08-09 불포화 탄화수소의 제조 방법 및 해당 방법에 사용되는 탈수소용 촉매
CN201180039002.6A CN103068774B (zh) 2010-08-12 2011-08-09 不饱和烃的制造方法和用于该方法的脱氢用催化剂
JP2012528676A JP5564115B2 (ja) 2010-08-12 2011-08-09 不飽和炭化水素の製造方法および当該方法に使用される脱水素用触媒
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WO2014053360A1 (fr) * 2012-10-01 2014-04-10 Evonik Degussa Gmbh Production de catalyseurs à base de boro-zéolites
WO2014099844A1 (fr) * 2012-12-19 2014-06-26 Shell Oil Company Catalyseur de déshydroaromatisation, son procédé de fabrication et d'utilisation
WO2016056403A1 (fr) * 2014-10-06 2016-04-14 Ｊｘ日鉱日石エネルギー株式会社 Procédé de fabrication de diène et catalyseur de déshydrogénation
WO2016056404A1 (fr) * 2014-10-08 2016-04-14 Ｊｘ日鉱日石エネルギー株式会社 Procédé de production de diène et catalyseur de déshydrogénation
JP2016188192A (ja) * 2015-03-30 2016-11-04 三井化学株式会社 ブタジエンを含む生成物の製造方法
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JP2017530078A (ja) * 2014-09-09 2017-10-12 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ホウ素およびチタンを含むｍｗｗゼオライト系材料の製造のための方法

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KR20130050963A (ko) 2013-05-16
JPWO2012020743A1 (ja) 2013-10-28
CN103068774B (zh) 2015-05-20
EP2604590A1 (fr) 2013-06-19
SG187797A1 (en) 2013-03-28
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US20130158328A1 (en) 2013-06-20
TW201210691A (en) 2012-03-16

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